Early Metal Di(pyridyl) Pyrrolide Complexes with Second Coordination Sphere Arene−π Interactions: Ligand Binding and Ethylene Polymerization

Early metal complexes supported by hemilabile, monoanionic di­(pyridyl) pyrrolide ligands substituted with mesityl and anthracenyl groups were synthesized to probe the possibility of second coordination sphere arene−π interactions with ligands with potential for allosteric control in coordination chemistry, substrate activation, and olefin polymerization. Yttrium alkyl, indolide, and amide complexes were prepared and structurally characterized; close contacts between the anthracenyl substituents and Y-bound ligands are observed in the solid state. Titanium, zirconium, and hafnium tris­(dimethylamido) complexes were synthesized, and their ethylene polymerization activity was tested. In the solid state structure of one of the Ti tris­(dimethylamido) complexes, coordination of Ti to only one of the pyridine donors is observed pointing to the hemilabile character of the di­(pyridyl) pyrrolide ligands.